Disazo pigments

ABSTRACT

Disazo dyestuffs of the formula

United States Patent Mueller et al. [451 Sept. 12, 1972 [54] DISAZO PIGMENTS [72] Inventors: Willy Mueller; Karl Ronco, both of Primary Examif'erejoseph Rebold Riehen; Rudolf Mary, Domach an Assistant Examiner- C. F Warren of Switzerland Stormy-Harry Goldsmlth, Joseph G. Kolodny and [73] Assignee: Ciba-Geigy AG, Basel, Switzerland am) Monaco [22] Filed: April 9, 1970 [57] ABSTRACT [21] APPL 271102 Disazo dyestuffs of the formula [30] Foreign Application Priority Data N R2COI:II:I $S.NHOCFR2 N April 25, 1969 Switzerland ..6360/69 in which R represents an ml residue, R2 represents a hydroxynaphthalene residue in which the 2120, hydroxy [52] 260/174 260/ ig: and --CO groups are in l, 2, 3-P0sition, or the residue of an enolized or enolizable ketomethylene compound gg gzg g ggi and R represents a phenylene or diphenylene residue o m containing at least onecarboxylic acid ester, carboxylic acid amide, sulphonic acid ester, sulphonic acid [56] References Cited amide or sulphone group are valuable pigments which UNITED STATES PATENTS are useful for coloring plastics and lacquers in yellow t d hades. 2,181,057 11/1939 Krzikalla et al ..260/184 re 8 3,262,925 7/1966 Mueller et al ..260/184 X 9 Claims, No Drawings 1 DISAZO PIGMENTS This invention is based on the observation that new and valuable disazo pigments of the formula s in which R, represents an aryl residue, R represents a hydroxynaphthalene residue in which the azo, hydroxy and -CO groups are in l, 2, 3-position or the residue of an enolized or enolizable ketomethylene compound and R, represents a phenylene or diphenylerie residue containing at least one carboxylic acid ester, carboxylic acid amide, sulphonic acid ester, sulphonic acid amide or sulphone group, may be obtained by condensing an azo dyestuff carboxylic acid halide of the formula R,N N R COl-lal with a diamine of the formula l-l,NR,,--Nl-l in a molar ratio of 2: l.

Since the products of the invention are pigments, they must not contain groups imparting solubility in water, especially acidic groups imparting solubility in water.

Pigments that are of special interest are those of the formula in which X, and Y, each represents a hydrogen or a halogen atom or an alkyl, alkoxy, phenoxy, nitro, cyano, carboxylic acid ester, acylamino, sulphone or trifluoromethyl group, Z, represents a hydrogen or a halogen atom or an alkyl, alkoxy or carboxylic acid amide group, X represents a hydrogen or a halogen atom or an alkoxy, cyano or nitro group, Y represents a carboxylic acid ester, carboxylic acid amide, sulphonic acid ester, sulphonic acid amide or sulphone group, Z represents a hydrogen or a halogen atom or an alkyl, alkoxy or phenoxy group, and n l or 2, and particularly those of the formula i'ifk in which X,, Y,, 2,, X and Y have the meanings given above, and particularly X, and Y, each represents hydrogen, chloro, bromo, lower alkyl, lower alkoxy, phenoxy, chlorophenoxy, loweralkyl phenoxy, nitro, cyano, lower carbalkoxy, carbophenoxy, carbochlorophenoxy, carbo-lower alkyl-phenoxy, carbonaphthoxy, lower alkyl-sulfonyl, or trifluoromethyl, Z, is hydrogen, chloro, bromo, lower alkyl, or lower alkoxy, X represents hydrogen, bromo, lower alkoxy, cyano or nitro, Y is lower carbalkoxy, carbophenoxy, carbo-chlorophenoxy, carbo-lower alkylphenoxy, carbonaphthoxy, sulfonic acid-lower alkyl ester, carboxylic acid amide, carboxylic acid-lower-alkyl amide, carboxylic acid-phenyl-amide, carboxylic acid-chlorophenyl amide, carboxylic acid-lower alkyl-phenyl amide, carboxylic acid-trifluorom'eth'ylphenyl amide, sulfonic acid amide, sulfonic acid-lower alkyl amide, sulfonic acid-phenyl-amide, sulfonic acid-chloro-phenyl amide, sulfonic acid-lower alkyl-phenyl amide, or lower alkyl sulfonyl, Z is hydrogen, chloro, lower alkyl or lower alkoxy or those of the formula chloroaniline, 3,4-dichloroaniline, 2,3-dichloroaniline,

2,4-dichloroaniline, 2,5-dichloroaniline, 2,6- dichloroaniline, 2,4,5-trichloroaniline, 2,4,6- trichloroaniline, 2-,' 3- or 4-bromoaniline, 2,4- dibromoaniline, 2,5-dibromoaniline, 2-, 3- or 4- methylaniline, 2,4-dimethylaniline, 2,5-

dimethylaniline, 2-methyl-5-chloroaniline, 2-methyl-4- chloroaniline, 2-methyl-3-chloroaniline, 2-chloro-5- trifluoromethylaniline, 2-, 3- or 4-nitroaniline, 2,4-

dinitroaniline, 3-trifluoromethylaniline, 3,5-bistrifluoromethylaniline, 2-chloro-5- trifluoromethylaniline, 4-chloro-2-nitroaniline, 2- chloro-4-nitroaniline, 4-methyl-2-nitroaniline, 4-

methyl-3-nitroaniline, 2,4-dimethyl-3-nitroaniline, 2- methyl-S-nitroaniline, 2-ethyl-5-nitroaniline, 2-methyl- 4-nitroaniline, 2-nitro-4-trifluoromethylaniline, 4-

nitro-Z -trifluoromethylaniline, 2- and 4-methoxyaniline, 3-chloro-4-methoxyaniline, 2-nitro-4-methoxyaniline, 2-nitr0-4-ethoxyaniline, 2-methoxy-5- nitroaniline, Z-methoxy-S-chloroaniline, 2,5-dimethoxy-4-chloroaniline, Z-methoxy-S-benzylsulphonylaniline, Z-methoxy-S-trifluormethylaniline, 2-ethylsulphonyl-S-trifluoromethylaniline, 2-amin0-4- trifluoromethyl-4-chlorodiphenylether, 2-amino-4- trifluoromethyldiphenylether, 2-amino-4- chlorodiphenylether, 2-amino-2'-dichlorodiphenylether, 2-amin0-4,4'-dichlorodiphenylether, laminobenzene-2-carboxylic acid methyl ester, 1- aminobenzene-Z-carboxylic acid ethyl ester, 1- aminobenzene-Z-chloro-S-carboxylic acid methyl ester, 2-amino-5-nitrobenzoic acid methyl ester, 1- amino-2-methylbenzene-5-carboxylic acid methyl ester, l-amino-2-chlorobenzene-S-carboxylic acid methylamide, 4-methyl-3-aminobenzoic acid amide, 4- chloro-3-aminobenzoic acid amide, 2,4-dichloro-- aminobenzoic acid amide, 4-methoxy-3-amin0benzoic acid amide, 4-methyl-3-aminobenzoic acid-2-chloro-5 '-trifluoromethyl-anilide, 4-chloro-3-aminobenzoic acid-2',5'-dichloroanilide, 4-chloro-3-aminobenzoic acid-2'-chlor0-5-carbomethoxyanilide, 4-chloro-3- aminobenzoic acid-3-chloroanilide, 2,4-dichl0r0-5- aminobenzoic acid-2',5-dichloroanilide, 2,4-dichloro- S-aminobenzoic acid-3'-trifluoromethylanilide, 2,4- dichloro-S-aminobenzoic acid-3'-chloroanilide, 5- amin0-4-methoxy-2-chlorobenz0ic acid-3'- trifluoromethylanilide, 4-methoxy-3-amin0ben2oic acid-3'-chloroanilide, 4-methoxy-3-aminobenzoic acid-2',5'-dichloroanilide, 4-carbomethoxy-3- aminobenzoic acid anilide, 4-methoxy-3-aminobenzoic acid-3'-trifluoromethyl-anilide, 4-carbethoxy-3- aminobenzoic acid-2',5'-dichl0r0anilide, 4- aminobenzoic acid-2,4-dichlorophenylamide, 4- aminobenzoic acid-2-chloro-5'-trifluor0methylphenylamide, 4-amino-3-methylbenzoic acid-3'-methylbenzoic acid-3'-trifluoromethylphenylamide, 4-amin0- 3-methylbenzoic acid-4-chlorophenylamide, 4-amino- 3-nitrobenz0ic acid-2',5'-dichlorophenylamide, l-

aminobenzene-S-sulphonic acid amide, laminobenzene-3-sulphonic acid methylamide, 1- aminobenzene-3-sulphonic acid ethylamide, l-

aminobenzene-3-sulphonic aminobenzene-3-sulphonic aminobenzene-Ii-sulphonic aminobenzene-3-sulphonic acid dimethylamide, acid diethylamide, acid phenylamide, acid morpholide,

aminobenzene-3-sulphonic acid piperidide, laminobenzene-4-sulphonic acid amide, lamin0benzene-4-sulphonic acid methylamide, laminobenzene-4-sulphonic acid ethylamide, l-

acid dimethylamide, acid diethylamide,

morpholide, l-amino-2-chlorobenzene-5-sulphonic acid phenylamide, l-amino-2,5-dichlorobenzene-4- sulphonic acid amide, l-amino-2,5-dichlorobenzene-4- sulfonic acid dimethylamide, l-amino-2,5- dichlorobenzene-4-sulphonic acid phenylamide, lamino-2-methylbenzene-5-sulphonic acid amide, lamino-2-methylbenzene-5-sulphonic acid methylamide, l-amino-2-methylbenzene-5-sulphonic acid dimethylamide, l-amino-2-methylbenzene-S-sulphonic acid phenylamide, l-amino-2-methylbenzene-5 sulphonic acid piperidide, l-amino-2-methylbenzene-5 -sulphonic acid benzylamide, l-amino-2-methylbenzene-5-sulphonic acid phenylamide, l-amino-2- methylbenzene-S-sulphonic acid-N-methyl-N-phenylamide, l-amino-2-methylbenzene-S-sulphonic acid-2- chlorophenylamide, l-amino-2-methylbenzene-5- sulphonic acid-4'-chlorophenylamide, l-amino-Z- methylbenzene-S-sulphonic acid-2',4 -dichlorophenylamide, l-amino-2-methylbenzene-5-sulphonic acid- 2'-methylphenylamide, l-amino-2-methylbenzene-5- sulphonic acid-4'-methylphenylamide, l-amino-2- methylbenzene-S-sulphonic acid-4-methoxyphenylamide, l-amin0-2-methylbenzene-S-sulphonic acid-4'- chloro-2'-methylamide, l-amino-2-methylbenzene-5- sulphonic acid-4'-chloro-3-methylamide, l-amin0-2- methylbenzene-S-sulphonic acid-3 trifluoromethylphenylamide, l-amino-2-methylbenzene-4-sulphonic acid-4'-chloro-2'-methylphenylamide, l-amino-Z-methylbenzene-4-sulphonic acid-4- phenylphenylamide, l-amino-2-methylbenzene-4- sulphonic acid dimethylamide, l-amino-2-methylbenzene-4-sulph0nic acid diethylamide, l-amin0-3- methylbenzene-4-sulphonic acid dimethylamide, lamino-2-methylbenzene-4-sulphonic acid phenylamide, l-amin0-4-methylbenzene-5-sulphonic acid amide, l-amino-4-methylbenzene-5 -sulphonic acid dimethylamide, l-amino-2-methoxybenzene-4- sulphonic acid amide, l-amino-2-methoxybenzene-4- sulphonic acid methylamide, l-amino-2-methoxybenzene-4-sulphonic acid dimethylamide, l-amino-Z- methoxybenzene-4-sulphonic acid phenylamide, lamin0-2-methoxybenzene-4-sulphonic acid-4- methylphenylamide, l-amino-Z-methoxybenzene-S- sulphonic acid amide, l-amino-2-methoxybenzene-S- sulphonic acid dimethylamide, l-amino-2-methoxybenzene-S-sulphonic acid phenylamide, l-amino-2- phenoxybenzene-4-sulphonic acid amide, l-amino-Z- phenoxybenzene-4-sulph0nic acid dimethylamide, 1- amino-2-phenoxybenzene-4-sulphonic acid phenylamide, laminO-Z-phenoxybenzene-S-sulphonic acid amide, l-amino-2-phenoxybenzene-5-sulphonic acid dimethylamide, l-amino-2-phenoxybenzene-5- sulphonic acid phenylamide, l-aminobenzene-2,4- disulphonic acid amide, l-aminobenzene-2,4-

disulphonic acid dimethylamide, l-aminobenzene-2,5- disulphonic acid amide, l-aminobenzene-2,5- disulphonic acid dimethylamide, l-aminobenzene-2,5 disulphonic acid phenylamide, l-aminonaphthalene, amino-4-phenoxynaphthalene, l-amino-8- chloronaphthalene, l-aminonaphthalene-3-sulph0nic acid amide, 1-aminonaphthalene-3-sulphonic acid methylamide, l-aminonaphthalene-3-sulphonic acid dimethylamide, l-aminonaphthalene-3-sulphonic acid phenylamide, l-aminonaphthalene-4-sulphonic acid amide, 1-aminonaphthalene-4-sulphonic acid methylamide, l -amino-naphthalene-4-sulphonic acid dimethylamide, 1-aminonaphthalene-4-sulphonic acid phenylamide, l-aminonaphthalene-5-sulphonic acid amide, l-aminonaphthalene-S-sulphonic acid dimethylamide, l-aminonaphthalene-5-sulphonic acid phenylamide, l-aminonaphthalene-6-sulphonic naphthalene-6-sulphonic acid amide, 1- aminonaphthalene-7-sulphonic acid amide, 2-

aminonaphthalene-S,7-disulphonic acid amide,- 2-- aminonaphthalene-6,8-disulphonic acid amide,

aminoanthraquinone and 2-aminoanthraquinone.

The azo dyestuff carboxylic acids thus obtained are treated with substances that are capable of converting carboxylic acids into their halides, for example their chlorides or bromides, such substances being, in particular, phosphorus halides, for example, phosphorus pentachloride, phosphorus trichloride or phosphorus pentabromide, phosphorus oxyhalides and preferably thionyl chloride.

The treatment with the saidacid halogenating agents is advantageously carried out in an inert organic solvent, for example, dimethylformamide, a chlorobenzene, for example, monochlorobenzene or dichlorobenzene, toluene, xylene or nitrobenzene. If necessary, dimethylformamide may be used in conjunction with the last five solvents specified. When preparing the carboxylic halides, it is generally advantageous first to dry the azo compounds, which are prepared in an aqueous medium, or to free them from water by azeotropic distillation in an organic solvent. If desired, azeotropic drying may be carried out immediately prior to the treatment with the said halogenating agents.

The azo dyestuff carboxylic acid halides obtained are condensed with diamines of the formula l-l N--R Nl-l preferably with those of the formula i Y lNHn fi l and particularly with those of the formula in which formulas R Y, Z, n and R have the meanings given above.

The following diamines are given as examples: 3,5- diaminobenzoic acid methyl ester, 3,5-diaminobenzoic acid ethyl ester, 3,5-diaminobenzoic acid butyl ester,

Z-aminonaphthalene-S-sulph0nic 3,5-diaminobenzoic acid phenyl ester, 3,5- diaminobenzoic acid-4-chlorophenyl ester, 3,5-

diaminobenzoic acid-2',4'-dichlorophenyl ester, 3,5- diaminobenzoic acid-2',4',5'-trichlorophenyl ester, 4- chloro-3,S-diaminobenzoicacid methyl ester, 4-chloro- 3,5-diaminobenzoic acid ethyl ester, 4.-chloro-3,5- diaminobenzoic acid propyl ester, 4-chloro-3,5- diaminobenzoic acid phenyl ester, 4-methyl-3,5- diaminobenzoic acid methyl ester, 4-methyl-3,5- diaminobenzoic acid ethyl ester, 4-methyl-3,5- diaminobenzoic acid phenyl ester, 4-methyl-3,5- diaminobenzoic acid-4'-methylphenyl ester, 4-methoxy-3,5-diaminobenzoic acid methyl ester, 4-methoxy- 3,5-diaminobenzoic acid ethyl ester, 4- methoxy-3,5- diaminobenzoic acid isopropyl ester, 4-methoxy-3,5- diaminobenzoic acid phenyl ester, 4-methoxy-3,5- diaminobenzoic acid cyclohexyl ester, 4-phenoxy-3,5- diaminobenzoic acid methyl ester, 4-'phenoxy-3,5- diaminobenzoic acid ethyl ester, 3,5-diaminobenzoic acid-B-naphthyl ester, 2-chloro-3,5-diaminobenzoic acid methyl ester, 2-chloro-3,S-diaminobenzoic acid ethyl ester, 2,5-diaminobenzoic acid methyl ester, 2,5- diaminobenzoic acid ethyl ester, 2,5-diaminobenzoic acid phenyl ester, 4-chloro-2,'5-diaminobenzoic acid methyl ester, 4-chloro-2,5-diaminobenzoic acid ethyl ester, 4-chloro-2,S-diaminobenzoic acid butyl ester, 4-

chloro-2,5-diamin0benzoic acid cyclohexyl ester, 4- methyl-Z,S-diaminobenzoic acid methyl ester, 4- methyl-2,5-diaminobenzoic acid ethyl ester, 4-methyl- 2,5-diaminobenzoic acid phenyl ester, 2,5- diaminobenzene-l,4-dicarboxylic acid methyl ester, 2,5-diaminobenzene-l ,4-dicarboxylic acid ethyl ester, 2,5-diaminobenzene-l,4-dicarboxylic acid propyl ester, 2,6-diaminobenzene-l,4-dicarboxylic acid methyl ester, 2,6-diaminobenzene-l,4-dicarboxylic acid ethyl ester, 2,4-diaminobenzoic acid methyl ester, 2,4-diaminobenzoic acid ethyl ester, 2,4- diaminobenzoic acid propyl ester, 4,4-diaminodiphenyl-carboxylic acid'methyl ester, 4,4"diaminodiphenyldicarboxylic acid ethyl ester, 4,4 -diaminodiphenyldicarboxylic acid propyl ester, 4,4-diaminodiphenyldicarboxylic acid butyl ester, 3,5-diaminobenzoic acid amide, 3,5-diaminobenzoic acid methylamide, 3,5- diaminobenzoic acid ethylamide, 3,5-diaminobenzoic acid phenylamide, 3,5-diaminobenzoic acid anilide, 3,5-diaminobenzoic acid-(4-methoxy)-anilide, 3,5- diaminobenzoic acid-(2',5'-dichloro)-anilide, 3,5- diaminobenzoic acid-(4'-chloro)-dianilide, 4-chloro- 3 ,S-diaminobenzoic acid anilide, 4-methyl-3 ,5- diaminobenzoic acid anilide, 4-methoxy-3 ,5- diaminobenzoic acid anilide, 4-phenoxy-3 ,5-

diaminobenzoic acid anilide, 2,5-diaminobenzoic acid amide, 2,5-diaminobenzoic acid methylamide, 2,5- diaminobenzoic acid ethylamide, 2,5-diaminobenzoic acid anilide, 4-chloro-2,S-diaminobenzoic acid anilide, 4-methyl-2,S-diaminobenzoic acid anilide, 2,5- diaminobenzene-l,4-dicarboxylic acid anilide, 3,5- diaminophenylmethylsulphone, 3,5-diaminodiphenylsulphone, 2,5-diaminophenylmethylsulphone, 2,5- diaminophenylethylsulphone, 2,5-diaminodiphenylsulphone, 3,5-diaminobenzenesulphonic acid methyl ester, 3,5-diaminobenzenesulphonic acid ethyl ester, 3,5-diaminobenzenesulphonic acid phenyl ester, 2,5- diaminobenzenesulphonic acid methyl ester, 2,5- diaminobenzenesulphonic acid ethyl ester, 2,5-

diaminobenzenesulphonic acid phenyl ester, 3,4- diaminobenzenesulphonic acid anilide, 3,4- diaminobenzenesulphonic acid-( 3 -trifluoromethyl anilide, 3,5-diaminobenzenesulphonic acid amide, 3,5-

diaminobenzenesulphonic acid methylamide, 3,5- diaminobenzenesulphonic acid ethylamide, 3,5- diaminobenzenesulphonic acid dimethylamide, 3,5- diaminobenzenesulphonic acid diethylamide, 3,5- diaminobenzenesulphonic acid phenylamide, 2,5- diaminobenzenesulphonic acid amide, 2,5- diaminobenzenesulphonic acid methylamide, 2,5 diaminobenzenesulphonic acid ethylamide, 2,5- diaminobenzenesulphonic acid dimethylamide, 2,5-

diaminobenzenesulphonic acid phenylamide and 2-(4'- methyl)-phenylsulphonyl-l ,4-diaminobenzene.

Condensation between the carboxylic acid halides defined above and the amines is advantageously carried out in an anhydrous medium. Under these conditions it generally proceeds surprisingly easily, even at temperatures within the boiling range of the common organic solvents, for example, toluene, monochlorobenzene, dichlorobenzene, trichlorobenzene, nitrobenzene and the like. To accelerate the reaction, it is generally advantageous to use an agent capable of binding acid, for example, anhydrous sodium acetate or pyridine. Some of the products obtained are crystalline and some are amorphous and they are generally obtained in a very good yield and in a pure state. It is expedient first to isolate the acid chlorides obtained from the carboxylic acids. In some cases, however, isolation of the acid chlorides may be omitted without harm and condensation may be carried out immediately after preparation of the carboxylic acid chlorides.

The new products are valuable pigments that may be used in a finely divided form for the coloration of organic materials of high molecular weight, for example, cellulose ethers, cellulose esters, polyamides, polyurethanes, polyesters, cellulose acetate, nitrocellulose, natural resins and synthetic resins, for example, polymerization resins or condensation resins, for example, aminoplasts, especially urea-formaldehyde and melamine formaldehyde resins, alkyd resins, phenoplasts, polycarbonates, polyolefines, for example, polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyacrylonitrile, polyacrylic acid esters, rubber, casein, and also for silicones and silicone resins. The pigments may be used single or in admixture with one another.

It is immaterial whether the compounds of high molecular weight specified above are used in the form of plastic compositions, melts, spinning solutions, lacquers or printing inks. Depending on the use, it is advantageous to use the new pigments as toners or in the form of preparations.

The following Examples illustrate the invention, the parts and percentages being by weight, unless otherwise stated.

EXAMPLE 1 36.1 Parts of the dyestuff obtained by coupling diazotized 2,5-dichloroaniline with 2,3-hydroxynaphthoic acid are treated for 3 hours at 110 to 120C with parts of thionyl chloride in 150 parts by volume of dichlorobenzene. The dyestuff acid chloride, which crystallizes in the form of shiny red needles after the batch has cooled, is isolated by filtration, washed successively with benzene and petroleum ether and then dried in vacuo at 40 to 45C. About 34 parts of the chloride are obtained, corresponding to 89.7 percent of the theoretical yield.

7.6 Parts of the dyestuff acid chloride so obtained are mixed with 250 parts of ortho-dichlorobenzene and then a solution of 3.0 parts of 4,4-diaminodiphenyl-3,3 '-dicarboxylic acid dimethyl ester in parts of orthodichlorobenzene and 0.2 part of pyridine is added at room temperature. The batch is then heated to to C during 2 hours and then stirred for 6 hours at that temperature. The batch is then allowed to cool to 100C, whereupon it is filtered and the filter residue is washed with ortho-dichlorobenzene having a temperature of 120C until the filtrate runs colorless. The filter residue is then washed successively with methanol and hot water, and dried in vacuo at 90 to 100C. 9.5 Parts (96.4 percent of the theoretical yield) of an orange pigment of the formula (JOOCHs are obtained. When the pigment is worked into polyvinyl chloride on a roller mill, it yields a brilliant orange coloration of high tinctorial strength and possessing excellent fastness to migration and light.

The 4,4'-diaminodiphenyl-3,3'-dicarboxylic acid dimethyl ester used in this Example may be obtained in the following manner:

200 Parts of sulphuric acid monohydrate are cooled to 0C and then 54.4 parts of 4,4'-diaminodiphenyl-3,3 -dicarboxylic acid are introduced at 0C while stirring. Dissolution first occurs, and then the sulphate precipitates after a short time in the form of grey crystals. 200 Parts of methanol are then run into the slurry of crystals, which can easily be stirred, without external cooling, in a manner such that the mixture, which heats up rapidly, just begins to reflux. The batch is then refluxed for 14 hours while stirring. The mobile reaction mixture is then cooled to room temperature, discharged on to 500 parts of ice, neutralized to pH 7 with sodium hydroxide solution at 0C, the pH is then adjusted to 10 with a 10 percent sodium carbonate solution, and the batch is filtered. The precipitate is washed with cold water until the washings run neutral and then dried in vacuo at 60 to 70C. This procedure yields 54 parts (90 percent of the theoretical yield) of 4,4'-diaminodiphenyl-3,3'-dicarboxylic acid dimethyl ester in the form of a light fawn powder melting at 187 to 190C. A single recrystallization from methanol is carried out and the compound is obtained in the form of small, pale yellow needles melting at 190 to 191C.

The following Table lists components for making further pigments. They can be obtained in the manner described above by coupling the diazo bases listed in column I with 2,3-hydroxynaphthoic acid, converting ments yield in polyvinyl chloride film are indicated in column lll.

ll .lll

l 2.5-dichloroaniline benzidine-3.3dicaryellowish boxylic acid diethyl orange ester 2 benzidine-3.3-dicarboxylic acid dibutyl ester 3 2,4,5-trichloroaniline benzidine-3.3'-dicarscarlet boxylic acid dimethyl ester 4 benzidine-3,3-dicar reddish boxylic acid diethyl orange ester 5 benzidine-3,3'-dicarorange boxylic acid dibutyl ester 6 2,4,-dichloro'aniline benzidine-3,3'-dicar-' yellowish boxylic acid dimethyl red ester 7 benzidine-Il.3'-dicar-' red' boxylic acid diethyl ester 8 2,4,6-trichloroaniline benzidine-3,3'-dicarboxylic acid dimethyl ester v 9 2.5-dibromoaniline benzidine-3,3'-dicarreddish boxylic acid dimethyl orange ester l 2-chloro-5-trifluoro benzidine-3,3'dicaryellowish methylaniline boxylic acid'dimethyl orange ester 1 l benzidine-3,3' -dicarorange boxylic acid dibutyl ester l2 4-chloro-3-trifluorobenzidine-3.3'-dicarmethylaniline boxylic acid dibutyl ester l3 4-trifluoromethyl-2- yellowish nitroaniline orange nitroaniline scarlet l 4-trifluoromethyl-2- amino-4'-chlorodiphenylether orange l6 Z-methyl-5-chlorobenzidine-3,3'-dicarred aniline boxylic acid dibutyl ester l7 benzidine-3,3'-dicarboxylic acid dimethyl ester 18 2-melhyl-3-chloro aniline l9 S-nitro-Z-methoxybluish aniline red 20 4-trifluoromethyl-2- yellowish amincbenzenel -ethylorange sulphone 21 dichloroaniline 2,5-diaminobenzoic acid orange ethyl ester methylaniline scarlet 23 2-methyl-3-chloro- 2.5-diaminobenzoic acid red aniline ethyl ester 24 2-methyl-4-chloroaniline 25 5-nitro-2-methoxy- 2.5-diaminobenzoic acid aniline methyl ester 26 2-nitro-4-trifluoromethylaniline 27 2.5-dichloroaniline 3,5-diaminobenzoic acid scarlet methyl ester 28 2.4,5-trichloroaniline k 29 Z-chloro-S-trifluoroyellowis methylaniline red 30 2-nitro-4-trifluoroorange methylaniline 3| 4-trifluoromethyl-2- yellowish aminobenzenel -methyl orange sulphone 32 Z-methyl-S-chloroaniline scarlet 33 2,4-dichloroaniline 34 S-nitro-Z-methoxyaniline red 35 2,4-dichloroaniline 36 2,4,5-trichloroaniline 37 Z-chloro-S-trifluoromethylaniline 38 4-trifluoromethyl-2- nitroaniline 39 2,5-dichloroaniline 40 2,4.5-trichloroaniline 41 2,4-dichloroaniline 42 4-trifluoromethyl-2- amino-4'-chlorodiphenyl ether 43 3-chloro-5-trifluoromethylaniline 44 2.5-dichloroaniline 4a 2,5-dichloroaniline 53 2,4,5-trichloroaniline 54 2-nitro-4-chloroaniline 55 2-amino-4-trifluoromethylbenzene-ethylsulphone 56 4-trifluoromethyl-2- amino-4'-chlorodiphenylether 57 2,5-dichloroaniline 6| anlline 62 2.4,5-trichloroaniline 63 v rt 66 4-trifluoromethyl-2- nitroaniline 68 4-methyl-3-aminobenzoic acid methyl ester 69 72 4-.methyl-3-aminobenzoic acid-(4 -methyl)-phenyl ester 73 4-methyl-3-aminobenzoic acid-fi-naphthyl ester 3.5-diaminobenzoic acid ethyl ester 4-methyl-3.S-diaminobenzoic acid methyl ester 4-methyl-3.5-diaminobenzoic acid ethyl ester 4-methyl-3,5-diaminobenzoic acid butyl ester 4-methyl-3,5-diaminobenzoic acid phenyl ester 4-chloro-3.5-diaminobenzoic acid ethyl ester 4-metl1oxy-3.5-diaminobenzoic acid ethyl ester 4-chloro-2,5-diaminobenzoic acid ethyl ester 4-methyl-2,5-diaminobenzoic acid ethyl ester 2,5-diaminobenzenel ,4- dicarboxylic acid diethyl ester 2,6-diaminobenzenel ,4- dicarboxylic acid diethyl ester 4-methyl-3,5-diaminobenzoic acid aniline 4-methoxy-3,5-diaminobenzoic acid anilide 4-chloro-3j-diaminov benzoic acid-4'--chloroanilide 2,5-diaminobenzoic acid anilide 2.5-diaminobenzoic acid -4'-chloroanilide 3,5-diaminobenzoic acid anilide 3,5-diaminobenzoic acid -(4-methoxy)-anilide 3,5-diarninobenzoic acid -(2,5'-dichloro)- anilide 3,4-diaminobenzoic acid -(4'-chloro)-anilide 3,4-diaminobenzene sulphonic acid-(3 trifluorornethyD- anilide 3,5-diaminobenzoic acid -(2'.5'-dichloro)- anilide 3,5-diaminobenzoic acid anilide 3,5-diaminobenzoic acid anilide 3,5-diaminobenzoic acid -(2',5'-dichloro)- anilide 3.5-diaminobenzoic acid -(4'-methoxy)-anilide 3,4-diaminobenzoic acid -(4'-chloro)-anilide 3,5-diaminobenzoic acid -(2',5'-dichloro)- anilide 3,5-diaminobenzoic acid scarlet reddish orange orange scarletred red scarlet orange scarlet red yellowish red bluish red orange scarlet orange scarlet bluish red orange brilliant scarlet red scarlet red brilliant orange orange scarlet yellowish orange scarlet brilliant orange red brilliant orange scarlet bluish red 75 4-methyl-3-aminobenzoic brilliant acid-(4'-methyl)-phenyl bluish ester red 76 4-methyl-3-aminobenzoic scarlet acid methyl ester 77 2 -dichloroaniline ben2idine-3,3'-dicarorange boxylic acid diamide 78 2,4.5-trichloroaniline yellowish brown 79 4-methoxy-3-aminored benzoic acid methyl ester 80 2-chloro-5-trifluoro- 3,5-diaminobenzoic acid orange methylaniline amide 8| 2 5-diaminobenzoic acid scarlet anilide 82 2 5-dichloroaniline 2,5-diaminobenzoic acid red dimethylamide 83 3,5-diaminobenzene scarlet sulphonic acid amide 84 3,5-cliaminobenzene sulphonic acid methylamide 85 a 3,5-diaminobenzene sulphonic acid anilide 86 2,4.5-trichloroaniline 3.5-diaminobenzoic acid reddish fl-naphthyl ester orange 87 3,5-diaminobenzoic acid -2'.4'.5'-trichloroanilide 88 4-trifluoromethyl-2- 3,5-diaminobenzoic acid yellowish nitroaniline -2'-chloro-5'-triorange fluoromethyl-anilide 89 3,5-diaminobenzoic acid -2',4',5'-trichloroanilide 90 2-amino-4-trifluorobenzidine-3,3'-dicarorange methyl-4'-chloroboxylic acid-dimethyl diphenyl ether ester 9l 2-amino-4-trifluoromethyldiphenyl ether 92 2-amino-4-trifluoromethy- 2',4'-dichloro-diphenyl ether 93 2-amino-4-trifluoromethyl- 2',4',5' ether 94 Z-amino-4-lrifluoromethyl- 2'-mcthyl-diphenyl ether 95 2amino-4-trifluoromethyl- 4-methyl-diphenyl ether 96 2-amino-4-trifluoromethyl- 4-tert.-butyl-diphenyl ether 97 4-amino-2-trifluoromethyldiphenyl ether scarlet 98 4-amino-Z-tril'luoromethyl- 4-chloro diphenyl ether EXAMPLE 2 19.8 Parts of the dyestuff carboxylic acid obtained by coupling diazotized 3amino-4-chlorobenzotrifluoride with 2,3-hydroxynaphthoic acid are heated for 30 minutes at 130 to 140C in 200 parts by volume of chlorobenzene together with 7.1 parts by volume of thionyl chloride. The solution so obtained is allowed to cool and the dyestuff carboxylic acid chloride crystallizes out in the form of needles. The product is isolated by filtration and dried in vacuo, the yield being 15.1 parts.

4.13 Parts of the acid chloride are heated for 12 hours at 130 to 140C in 150 parts by volume of orthodichlorobenzene together with 1.3 parts of the dichlorohydrate of Z-methylsulphonyll ,4- diaminobenzene and 1.4 parts by volume of triethylamine. A pigment is obtained in the form of fine crystals. it is isolated by filtration while hot, washed successively with hot ortho-dichlorobenzene, methanol and water and then dried. The pigment colors polyvinyl chloride a yellowish red shade possessing very good fastness to migration and good fastness to light. It has the formula N ll N C F: l

I SIO: CH:

N- iii NH-C O The following Table lists components for making further pigments. They can be obtained in the manner described above by coupling the diazo bases listed in column I with 2,3-hydroxynaphthoic acid, converting the azo dyestuff carboxylic acids so obtained into their acid chlorides, and then condensing the latter with the diamines given in column II. The shades that the pig ments yield in polyvinyl chloride film are indicated in column "I.

The following Table lists components for making further pigments. They may be obtained in the manner described above by coupling the diazo bases listed in column I with the hydroxynaphthoic acid listed in column ll, converting the azo dyestuff carboxylic acids so obtained into their acid chlorides and then eondensing the latter with the diamines listed in column Ill. The shades that the pigments yield in polyvinyl chloride film are indicated in column IV.

I ll III IV I 2.5-dichloro- 6-bromo-2,3-hydroxybenzidine-3,3' scarlet aniline naphthoic acid -dicarboxylic acid dimethyl ester 2 6-methoxy-2,3- benzidine-3,3'- red dicarboxylic acid hydroxy-naphthoic acid diethyl ester 3 2,5-diaminoclaret 1 berizoic acid Y1 anilide N 4 5 6-nitro-2,3-hydroxybenzidine-3,3 red H naphthoic acid dicarboxylic acid 1 21 N dimethyl ester 5 5 6-cyano-2.3-hydroxynaphthoic acid C 0 OR I We claim: A

1'. A disazo pigment of the formula X1 in which X, X Y and Z.- have the meanings given in X1 Y1 claim Zand R- represents a lower alkyl group.

, 22 N 4. The compound asclaimed'in claim 1 of the formux -coNH- 1 n 011 000mm v in which X and Y .each represents hydrogen, chloro, 3 bromo, lower alkyl, lower alkoxy', phenoxy, chlorophenoxy, loweralkyl phenoxy, nitro, cyano, H lower carbalko'xy, carbophenoxy, carbochlorophe'noxy, carbo-lower alkyl-phenoxy, carbonaphthoxy, lower 25 G alkyl-sulfonyl, or trifluoromethyl, Z is hydrogen, chloro, bromo, lower alkyl, or lower alkoxy, X C000 H HO represents hydrogen, brom'o; lower alkoxy, cyano or r 2 nitro, Yis lower carbalkoxy, carbophenoxy, carbochlorophenoxy, carbo-lower alkyl-phenoxy, carbonaphthoxy, sulfonic acid-lower alkyl ester, carboxylic acid amide, carboxylic acid-l'ower-alkyl amide, carboxylic acid-phenyl-amide, v carboxylic acidchlorophenyl amide, carboxylic acid-'lower-alkyl-phenyl amide, carboxylic acidtrifl'uoromethyl-pheny] amide, sulfonic acid amide, sulfonic acid-lower alkyl amide, sulfonic acid-phenyl-amide, sulfonic acidchloro-phenyl amide, sulfonic acid-lower alkyl-phenyl amide, or lower alkyl sulfonyl, Z is hydrogen, chloro, 40 lower alkyl or lower alkoxy and n is l or 2.

2. A disazo pigment, as claimed in claim 1 of the formula 30 I NHOC 5. The compound as claimed in claim 1 of the form ula x i a Y1 Y1 1 .v

-OH Y N no A} 1% X CONH I F:

NHOC X 000011 HO 7 Z.

I H0 in which X Y,, 2,, X, Y and Z have the meanings N 0 given in claim 1.

3. A disazo pigment as claimed in claim 1 of the formula 6. The compound as claimed in claim 1 of the form ui la N N 1% 2 ii I 1 0 F3 OH COOR OH I (500011;

X 4M0 ME 310201115 C1 C1 Q" KI} Q 1: 1i FaC 5 c 111 0 F; 200cm no -on no- O-NHOC -o 0NII- N[I()C 7. The compound as claimed in claim 1 of the formul0 la 000mm 9. The compound as claimed in claim I of the formu- OI'I lIO- C ONH- N1100- COUCH:

8. The compound as claimed in claim 1 of the formula 

2. A disazo pigment, as claimed in claim 1 of the formula
 3. A disazo pigment as claimed in claim 1 of the formula
 4. The compound as claimed in claim 1 of the formula
 5. The compound as claimed in claim 1 of the formula
 6. The compound as claimed in claim 1 of the formula
 7. The compound as claimed in claim 1 of the formula
 8. The compound as claimed in claim 1 of the formula
 9. The compound as claimed in claim 1 of the formula 